US6723298B1 - Method for catalytic conversion of carbon monoxide in a hydrogen-containing gas mixture - Google Patents

Method for catalytic conversion of carbon monoxide in a hydrogen-containing gas mixture Download PDF

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Publication number
US6723298B1
US6723298B1 US09/568,814 US56881400A US6723298B1 US 6723298 B1 US6723298 B1 US 6723298B1 US 56881400 A US56881400 A US 56881400A US 6723298 B1 US6723298 B1 US 6723298B1
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catalyst
carbon monoxide
gas mixture
space velocity
conversion
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Expired - Fee Related
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US09/568,814
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Frank Baumann
Stefan Wieland
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DMC2 Degussa Metals Catalysts Cerdec AG
Umicore AG and Co KG
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DMC2 Degussa Metals Catalysts Cerdec AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a method for catalytic conversion of carbon monoxide with water to carbon dioxide and hydrogen in a gas mixture that contains hydrogen and other oxidizable components.
  • reaction in accordance with reaction equation (1) is called carbon monoxide conversion or CO conversion herein.
  • water gas shift reaction is commonly used for this in the USA.
  • Catalysts for the conversion of carbon monoxide in accordance with reaction equation (1) are also called shift catalysts herein.
  • These known catalysts are complete catalysts that contain non-noble metals. They are used in two-stage processes. In the first process stage a so-called high temperature CO conversion (high temperature water-gas shift, HTS) is carried out on Fe/Cr catalysts at temperatures between 360 and 450° C. In the subsequent second stage a low-temperature CO conversion (low temperature water-gas shift, LTS) is undertaken on Cu/ZnO catalysts at temperatures between 200 and 270° C. After the low temperature process stage carbon monoxide concentrations of less than 1 vol % in correspondence with the thermal equilibrium are obtained.
  • HTS high temperature water-gas shift
  • LTS low-temperature CO conversion
  • Both the known high-temperature and the low-temperature catalysts are bulk catalysts, in which the catalyst material is pressed to form pellets or other molded bodies. Accordingly, they consist entirely of catalytically active mass and are also called complete catalysts. As a rule, they have a very high bulk weight.
  • reaction equation (1) The known industrial methods for conversion of carbon monoxide on catalysts according to reaction equation (1) operate at space velocities of the gas mixture between 300 and 3000 h ⁇ 1 . These low velocities are not sufficient for use in motor vehicles.
  • R CO for the carbon monoxide, which is understood within the scope of this invention to mean the amount of carbon monoxide N CO converted per weight of the catalyst m cat and reaction time ⁇ t.
  • the known Cu/ZnO and Fe/Cr catalysts have to be activated by reduction before they are used.
  • the activated catalysts are sensitive to oxygen. Upon contact with atmospheric oxygen they are reoxidized and deactivated in an exothermic reaction.
  • noble metal catalysts for these uses are also known, mainly from the scientific literature.
  • the known complete catalysts in the form of tablets, pellets or irregularly shaped particles are used as so called bulk catalysts. Only unsatisfactory space-time yields are obtained with such catalysts. In addition, the achievable specific conversion rates with these catalysts are low.
  • an object of the present invention is to provide a method for conversion of carbon monoxide in a hydrogen-containing gas mixture that, under the conditions of mobile use in motor vehicles with their rapidly changing power requirements, a high specific conversion rate for carbon monoxide with good selectivity, has high temperature stability and is insensitive to oxygen in the educt gas mixture.
  • a method for catalytic conversion of carbon monoxide to carbon dioxide and hydrogen (carbon monoxide conversion) in a hydrogen-containing gas mixture For conversion of the carbon monoxide, the gas mixture is passed over a shift catalyst, which is at the operating temperature for carbon monoxide conversion.
  • the method features a shift catalyst based on noble metals that is applied to an inert carrier in the form of a coating.
  • the method of the present invention is specifically directed to mobile use in motor vehicles powered by fuel cells in order to effectively removed carbon monoxide from the hydrogen-rich gas mixture that is obtained by steam reforming, partial oxidation or autothermic reforming (hereinafter also called reformate gas) under all conditions of operation of the motor vehicle.
  • the gas mixture can contain up to 40 vol % carbon monoxide, depending on its production.
  • the mobile use of the method imposes high requirements on its efficiency and dynamics.
  • the catalysts are loaded with very different space velocities. They vary between a low space velocity at idling and 100,000 h ⁇ 1 at full load.
  • the method of the invention enables a high efficiency, i.e., a high space-time yield through the application of the catalyst in the form of a coating onto an inert carrier.
  • a catalyst is also called a coating catalyst herein.
  • the monolithic honeycomb elements of ceramic or metal with cell densities (number of flow channels per area of cross section) of more than 10 cm ⁇ 2 that are known from auto exhaust treatment are suitable as carrier.
  • metal sheet, heat exchanger plates, open-cell ceramic or metal foam elements and irregularly shaped elements formed in each case according to requirements can also be used as carriers.
  • the thickness of the coating can vary between 10 and 100 ⁇ m according to application.
  • a carrier within the scope of this invention is characterized as inert if the material of the carrier does not participate or participates only negligibly in the catalytic conversion. As a rule, these are bodies with low specific surface and low porosity.
  • a catalyst that contains the elements of the platinum group of metals, thus platinum, palladium, rhodium, iridium, ruthenium and osmium, or gold as the catalytic active components on an oxide support made from the group consisting of aluminum oxide, silicon dioxide, titanium oxide, rare earth oxides or mixed oxides of these or zeolites is suitable for the proposed method.
  • the support material should have at least a specific surface (BET surface, measured in accordance with DIN 66132) of more than 10 m 2 /g.
  • This noble metal catalyst exhibits a shift activity, i.e., it is capable, if the appropriate reaction conditions exist (temperature, gas composition), of converting carbon monoxide with water in accordance with reaction equation (1) to carbon dioxide and hydrogen. For this reason it is also called a noble metal shift catalyst herein. Its shift activity and selectivity can be improved by the addition of other catalytically active components, or promoters. Among these are elements of the rare earth metals, in particular cerium and lanthanum, as well as the non-noble metals of the subgroups of the periodic system of elements, especially iron or copper.
  • the shift activity and selectivity can, moreover, also be increased by doping the support material with redox-active oxides of the metals cerium, zirconium, titanium, vanadium, manganese and iron in an amount of 1 to 50 wt % with respect to the total weight of the support material.
  • a preferred shift catalyst for the method in accordance with the invention contains platinum and/or palladium together with iron or copper as well as cerium oxide on a finely divided aluminum oxide.
  • the use of the shift catalyst based on noble metals for the method also has the advantage that this catalyst does not become deactivated by contact with oxygen. For this reason no costly measures to protect the catalyst from contact with air are necessary in a motor vehicle.
  • the described catalyst material is not processed to complete catalysts, but rather is applied in the form of a coating to inert supports.
  • the disadvantages of complete catalysts that consist of the catalytically active centers in the interior of the complete catalyst being poorly accessible to the reactants are avoided in this method. Poor accessibility reduces the specific conversion rate for carbon monoxide and thus the achievable space-time yield. This has the corresponding negative effects on the volume of the required reactor.
  • the vibrations caused by operation of the motor vehicle additionally lead to undesired abrasion of complete catalysts, which blocks the flow paths in the catalyst bed and thus continuously increases the pressure difference in the reactor.
  • the process operates at gas mixture space velocities from idling space velocity up to a value of 100,000 h ⁇ 1 and at a pressure between atmospheric pressure and 10 bar, where the space velocity is given in reference to the volume of carrier coated with the catalyst.
  • the method can be used both for low-temperature CO conversion as well as for high-temperature CO conversion.
  • a noble metal shift catalyst with an operating temperature between 180 and 300° C. is used for the low-temperature CO conversion.
  • the low operating temperature is achieved through a relatively high charge of catalytically active noble metals on the catalyst.
  • the reformate gas usually contains 2 to 15 vol % carbon monoxide and has an input temperature between 100 and 250° C., which results from the reforming process.
  • a noble metal shift catalyst with an operating temperature between 280 and 550° C. is used for the high temperature CO conversion.
  • the reformate gas usually contains 2 to 40 vol % carbon monoxide and has an input temperature between 300 and 600° C., which results from the reforming process.
  • the method also allows a high temperature conversion stage and a low temperature conversion stage to be connected in succession.
  • the gas mixture in this case leaves the high temperature stage at a temperature that corresponds to the operating temperature of the catalyst of the high temperature stage and for this reason has to be cooled to the operating temperature of the catalyst of the low-temperature stage before contact with it.
  • the support material for the catalytically active components can be suspended in an aqueous solution of soluble compounds of a noble metal selected from the group consisting of platinum, palladium, rhodium, ruthenium, iridium, osmium, gold and mixtures thereof and other soluble compounds of non-noble metals of the subgroups.
  • a noble metal selected from the group consisting of platinum, palladium, rhodium, ruthenium, iridium, osmium, gold and mixtures thereof and other soluble compounds of non-noble metals of the subgroups.
  • the acid suspension is neutralized at elevated temperature with a base, for example, a sodium carbonate, and then reduced at the same temperature with an aqueous reducing agent (formaldehyde, hydrazine), filtered, washed, dried, calcined in an oxidizing atmosphere at temperatures between 300 and 550° C., and then reduced at temperatures between 300 and 600° C.
  • a base for example, a sodium carbonate
  • an aqueous reducing agent formaldehyde, hydrazine
  • the catalyst material is again suspended in water to produce a coating suspension.
  • the carrier element is coated with this suspension.
  • the methods for coating carrier elements that are known from auto exhaust catalysis can be used.
  • the coating is dried, calcined at temperatures between 300 and 600° C. and reduced in a hydrogen-containing gas at temperatures between 300 and 600° C.
  • the carrier element is first coated only with the support material, where the support material can contain rare earth oxides and oxides of non-noble metals of the subgroups.
  • the coating on the carrier element is then impregnated with a solution of at least one soluble noble metal compound, soluble compounds of the rare earths and the non-noble metals of the subgroups.
  • the coated carrier element is dried, calcined at temperatures between 300 and 600° C. and reduced in a hydrogen-containing gas at temperatures between 300 and 600° C.
  • Another variation for making a coating catalyst in accordance with the invention resides in first producing a suspension of the support material, the soluble compounds of the noble metals and optionally the soluble compounds of the non-noble metals of the subgroups and the rare earths. The dissolved components of the suspension are then precipitated onto the suspended support material through the addition of a basic precipitation agent such as sodium hydroxide. The suspension prepared in this way is used directly for coating the carrier element. To finish the production of the coating catalyst, the coated carrier element is dried, calcined at temperatures between 300 and 600° C. and reduced in a hydrogen-containing gas at temperatures between 300 and 600° C.
  • a noble metal shift catalyst (catalyst A) was produced as follows:
  • a ceramic element honeycomb carrier with 93 cells per square centimeter and a volume of 0.041 L was coated with 7.25 g ⁇ -aluminum oxide by immersing it in an aqueous suspension of ⁇ -aluminum oxide (specific surface 140 m 2 /g) and calcining for 2 h at 600° C. After calcination the coated honeycomb element was impregnated with a solution of Ce(NO 3 ) 2 .6H 2 O and then calcined for 2 h at 500° C. The calcined molded element was then impregnated with a solution of Pt(NO 3 )2, Pd(NO 3 ) 2 and Fe(NO 3 ) 3 .
  • the catalytically active coating of the catalyst prepared in this way had a total weight of 5.16 g, which corresponds to 126 g per liter of volume of the honeycomb element. It contained 1.2 wt % Pt, 1.2 wt % Pd, 2.4 wt % Fe, 35.7 wt % CeO 2 and 59.5 wt % Al 2 O 3 .
  • the catalyst was tested under the conditions of a high temperature conversion with a synthetic reformate. Its CO 2 selectivity S CO2 , CO conversion, as well as specific conversion rate R CO in accordance with equation (4) were measured.
  • the following gas composition was used for the high temperature conversion: 27.0 vol % H 2 , 9.0 vol % CO, 9.0 vol % CO 2 , 18.0 vol % H 2 O, 37.0 vol % N 2 .
  • catalyst B A commercial Fe/Cr catalyst (catalyst B; tablets 5 ⁇ 5 mm) was tested under the same conditions as catalyst A.
  • German priority application 100 13 895.0 is relied on and incorporated herein by reference.

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US09/568,814 2000-03-21 2000-05-11 Method for catalytic conversion of carbon monoxide in a hydrogen-containing gas mixture Expired - Fee Related US6723298B1 (en)

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Applications Claiming Priority (2)

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DE10013895 2000-03-21
DE10013895A DE10013895A1 (de) 2000-03-21 2000-03-21 Verfahren zur katalytischen Umsetzung von Kohlenmonoxid in einem Wasserstoff enthaltenden Gasgemisch

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JP (1) JP4819235B2 (da)
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Cited By (24)

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US20020122764A1 (en) * 2000-09-25 2002-09-05 Lawrence Shore Platinum group metal promoted copper oxidation catalysts and methods for carbon monoxide remediation
US20040058810A1 (en) * 2000-03-21 2004-03-25 Frank Baumann Method for catalytic conversion of carbon monoxide in a hydrogen-containing gas mixture
US20040175491A1 (en) * 2002-12-20 2004-09-09 Alfred Hagemeyer Methods for the preparation of catalysts for hydrogen generation
US20040175325A1 (en) * 2002-12-20 2004-09-09 Alfred Hagemeyer Alkali-containing catalyst formulations for low and medium temperature hydrogen generation
US20040175327A1 (en) * 2002-12-20 2004-09-09 Alfred Hagemeyer Catalyst formulations containing group 11 metals for hydrogen generation
US20040176245A1 (en) * 2002-12-20 2004-09-09 Alfred Hagemeyer Noble metal-free nickel catalyst formulations for hydrogen generation
US6790432B2 (en) * 2002-06-12 2004-09-14 Engelhard Corporation Suppression of methanation activity of platinum group metal water-gas shift catalysts
US20040177556A1 (en) * 2002-12-20 2004-09-16 Alfred Hagemeyer Platinum and rhodium and/or iron containing catalyst formulations for hydrogen generation
US20040180784A1 (en) * 2002-12-20 2004-09-16 Alfred Hagemeyer Platinum-free ruthenium-cobalt catalyst formulations for hydrogen generation
US20040180000A1 (en) * 2002-12-20 2004-09-16 Alfred Hagemeyer Platinum-ruthenium containing catalyst formulations for hydrogen generation
US20040184986A1 (en) * 2002-12-20 2004-09-23 Alfred Hagemeyer Platinum-alkali/alkaline-earth catalyst formulations for hydrogen generation
US20040191164A1 (en) * 2003-02-05 2004-09-30 Niels Christian Schiodt Process and catalyst for treatment of synthesis gas
US20050207958A1 (en) * 2004-03-18 2005-09-22 Anca Faur-Ghenciu High activity water gas shift catalysts with no methane formation
US20050276741A1 (en) * 2004-06-10 2005-12-15 Chevron U.S.A. Inc. Method for making hydrogen using a gold containing water-gas shift catalyst
US20060128565A1 (en) * 2002-11-07 2006-06-15 Maria Flytzani-Stephanopoulos Catalyst having metal in reduced quantity and reduced cluster size
US20060182679A1 (en) * 2005-02-16 2006-08-17 Ilinich Oleg M Precious metal water-gas shift catalyst with oxide support modified with rare earth elements
US20070299444A1 (en) * 2004-08-26 2007-12-27 Endius, Inc. Methods and apparatus for access to and/or treatment of the spine
US20070298963A1 (en) * 2006-05-04 2007-12-27 Thompson Levi T Reducible oxide based catalysts
US20080233045A1 (en) * 2005-06-15 2008-09-25 The Ohio State University Catalyst for Hydrogen Production From Water Gas Shift Reaction
US20080274878A1 (en) * 2005-12-23 2008-11-06 Sk Energy Co. Ltd Platinum Based Catalyst for Oxidation/Reduction Reaction and Its Use
US7704918B2 (en) 2005-05-19 2010-04-27 Brookhaven Science Associates, Llc Synthesis of metal-metal oxide catalysts and electrocatalysts using a metal cation adsorption/reduction and adatom replacement by more noble ones
US20110207003A1 (en) * 2007-08-10 2011-08-25 Sud-Chemie Ag Method for removing CO, H2 and/or CH4 from the anode waste gas of a fuel cell with mixed oxide catalysts comprising Cu, Mn and optionally at least one rare earth metal
US8834835B2 (en) * 2008-03-14 2014-09-16 Clariant Corporation Ultra high temperature shift catalyst with low methanation
US11447434B2 (en) * 2018-03-13 2022-09-20 Nova Chemicals (International) S.A. Mitigating oxygen, carbon dioxide and/or acetylene output from an ODH process

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DE10013894A1 (de) * 2000-03-21 2001-10-04 Dmc2 Degussa Metals Catalysts Verfahren zur katalytischen Umsetzung von Kohlenmonoxid in einem Wasserstoff enthaltenden Gasgemisch mit verbessertem Kaltstartverhalten und Katalysator hierfür
WO2002016260A1 (en) * 2000-08-18 2002-02-28 Matsushita Electric Industrial Co., Ltd. Hydrogen purification apparatus
JP4663095B2 (ja) * 2000-10-23 2011-03-30 パナソニック株式会社 水素精製装置
EP1354853A4 (en) 2001-01-26 2009-08-19 Panasonic Corp HYDROGEN PURIFICATION DEVICE AND FUEL CELL POWER GENERATION SYSTEM
JP4867084B2 (ja) * 2001-06-12 2012-02-01 パナソニック株式会社 水素精製装置
KR100460433B1 (ko) * 2001-12-11 2004-12-08 (주)에너피아 개질가스 정제용 촉매 및 이를 이용하여 수소가 풍부한개질가스 내의 일산화탄소를 선택적으로 제거하는 방법
US7001867B2 (en) * 2002-05-21 2006-02-21 Conocophillips Company Rare earth aluminates and gallates supported rhodium catalysts for catalytic partial oxidation of hydrocarbons
US7265076B2 (en) 2002-12-26 2007-09-04 Matsushita Electric Industrial Co, Ltd. CO removal catalyst, method of producing CO removal catalyst, hydrogen purifying device and fuel cell system
US20070183968A1 (en) * 2005-08-03 2007-08-09 Todd Healey Water-gas shift and reforming catalyst and method of reforming alcohol
KR100723394B1 (ko) * 2006-02-07 2007-05-30 삼성에스디아이 주식회사 비자연발화성 쉬프트 반응 촉매 및 그의 제조 방법
US8877674B2 (en) * 2006-04-26 2014-11-04 Battelle Memorial Institute Selective CO methanation catalysis
GB201505556D0 (en) * 2015-03-31 2015-05-13 Johnson Matthey Plc Catalysts
WO2018095882A1 (en) 2016-11-22 2018-05-31 Umicore Ag & Co. Kg Iron containing catalyst

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